EP3235588A1 - Solder alloy for plating and electronic component - Google Patents
Solder alloy for plating and electronic component Download PDFInfo
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- EP3235588A1 EP3235588A1 EP15869874.6A EP15869874A EP3235588A1 EP 3235588 A1 EP3235588 A1 EP 3235588A1 EP 15869874 A EP15869874 A EP 15869874A EP 3235588 A1 EP3235588 A1 EP 3235588A1
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- solder alloy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0016—Brazing of electronic components
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/08—Tin or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
- H05K1/111—Pads for surface mounting, e.g. lay-out
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/36—Electric or electronic devices
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
- H05K1/118—Printed elements for providing electric connections to or between printed circuits specially for flexible printed circuits, e.g. using folded portions
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/07—Electric details
- H05K2201/0753—Insulation
- H05K2201/0769—Anti metal-migration, e.g. avoiding tin whisker growth
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/4007—Surface contacts, e.g. bumps
Definitions
- the present invention relates to a solder alloy for plating used for an electric contact that establishes electric continuity by mechanical joining, particularly to a solder alloy for plating and an electronic component used in a fitting type connection terminal.
- surfaces of wiring materials are plated with tin (Sn), silver (Ag), gold (Au) or nickel (Ni) in order to prevent the wiring materials from oxidizing.
- Sn is inexpensive, and owing to its softness, readily deforms when receiving pressure upon fitting (contacting), leading to an increased contact area and a lower contact resistance. Accordingly, wiring materials with Sn-plated surfaces are widely and typically used.
- a whisker generated at an electric contact due to an external stress applied through mechanical joining is also called “external stress-type whisker.”
- whiskers generated due to different causes from those of generation of external stress-type whiskers known are an "internal stress-type whisker (naturally-generated whisker)" generated due to volume expansion associated with the growth of an intermetallic compound in Sn plating, a “temperature cycle-type whisker” generated due to a compressive stress resulting from the difference in thermal expansion between a substrate and Sn plating, and an “oxidation/corrosion-type whisker” generated due to a compressive stress resulting from oxidation or corrosion of Sn in a high temperature and high humidity environment.
- an "internal stress-type whisker naturally-generated whisker
- a temperature cycle-type whisker generated due to a compressive stress resulting from the difference in thermal expansion between a substrate and Sn plating
- oxidation/corrosion-type whisker generated due to a compressive stress resulting from oxidation or corrosion of Sn in a high temperature and high humidity environment.
- Patent Literature 1 describes, as a solder alloy capable of eliminating the problem associated with external stress-type whiskers, "a Pb-free solder alloy comprising: Ag of 0.1 to 5 wt%; Cu of 0.1 to 5 wt%; a first dopant of not more than 10 wt%, the first dopant comprising at least one element selected from a group consisted of Sb, Bi, Cd, In, Ag, Au, Ni, Ti, Zr, and Hf; a second dopant of not more than 10 wt%, and the second dopant comprising at least one element selected from a group consisted of Ge, Zn, P, K, Cr, Mn, Na, V, Si, Al, Li, Mg and Ca; and Sn as a remaining part" ([claim 10]).
- a Pb-free solder alloy comprising: Ag of 0.1 to 5 wt%; Cu of 0.1 to 5 wt%; a first dopant of not more than 10 wt%, the first
- Patent Literature 2 describes "a Pb-free solder alloy comprising: not less than 0.1 wt% but not more than 3.5 wt% of Ag; not less than 0.1 wt% but not more than 3.5 wt% of Cu; not less than 0.002 wt% but not more than 0.5 wt% of Zn; and the balance of Sn" and "the Pb-free solder alloy obtained by adding at least one of P, Ge, K, Cr, Mn, Na, V, Si, Ti, Al, Li, Mg, Ca and Zr as an oxidation control element" ([claim 10] and [claim 11]).
- Patent Literatures 1 and 2 The present inventors have made a study on the Pb-free solder alloys described in Patent Literatures 1 and 2 and found that some types and combinations of added metals do not serve to sufficiently suppress the generation of external stress-type whiskers.
- An object of the present invention is therefore to provide a solder alloy for plating and an electronic component that are capable of suppressing the generation of external stress-type whiskers.
- the present inventors have made an intensive study to achieve the object above and found that by adding a specific amount(s) of Ni and/or Co in addition to Sn, the generation of external stress-type whiskers can be suppressed.
- the invention has been thus completed.
- the present inventors found that the object can be achieved by the characteristic features as described below.
- the present invention is able to provide a solder alloy for plating and an electronic component that are capable of suppressing the generation of external stress-type whiskers.
- solder alloy for plating and the electronic component according to the invention are described below.
- any numerical range using “to” refers to a numerical range including the values stated before and after “to” as the upper and lower limits, and the sign “%” for the content refers to % by mass.
- a solder alloy for plating according to a first embodiment of the invention used for an electric contact that establishes electric continuity by mechanical joining comprises Sn and Ni, wherein the Ni content is not less than 0.06 wt% but not greater than 5.0 wt%, and the balance is Sn.
- a solder alloy for plating according to a second embodiment of the invention used for an electric contact that establishes electric continuity by mechanical joining comprises Sn and Co, wherein the Co content is not less than 0.01 wt% but less than 8 wt%, and the balance is Sn.
- a solder alloy for plating according to a third embodiment of the invention used for an electric contact that establishes electric continuity by mechanical joining comprises Sn, Ni and Co, wherein the total content of Ni and Co is less than 9.5 wt%, the Ni content and the Co content are each greater than 0 wt% and at least one of the requirement that the Ni content is not less than 0.03 wt% and the requirement that the Co content is not less than 0.010 wt% is satisfied, and the balance is Sn.
- solder alloy of the invention each contain a specific amount(s) of Ni and/or Co in addition to Sn, the generation of external stress-type whiskers is suppressed.
- the present inventors assumed that external stress-type whiskers are generated because Sn atoms contained in a plating film are dispersed due to a mechanical stress applied from the outside and subsequently, the Sn atoms are recrystallized, resulting in the generation of whiskers, which are whisker-like crystals.
- the present inventors then assumed that when a specific amount(s) of Ni and/or Co is contained in addition to Sn, a Sn-Ni compound, a Sn-Co compound or a Sn-Ni-Co compound is to be present in a plating film, which serves to inhibit the dispersion of Sn atoms, leading to a decrease in growth and even generation of whiskers.
- the present inventors found that, with Sn plating using a solder alloy containing a specific small amount of Ni, the generation of internal stress-type whiskers mentioned above is unable to be suppressed. Considering this finding, it can be said that the fact that the solder alloy of the invention brings about the effect of suppressing the generation of external stress-type whiskers is totally unforeseeable.
- the Ni content is not less than 0.06% but not greater than 5.0%.
- Ni is an element that influences the suppression of generation of whiskers and the occurrence of fractures and cracks. With a Ni content of less than 0.06%, the effect of suppressing the generation of whiskers is not exhibited.
- the Ni content is preferably less than 5.0% for the sake of, inter alia, heat resistance of an electronic component in cases where a plating film is formed by hot dipping and appearance of a plating film in cases where the plating film is formed by electroplating.
- the Ni content is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably not less than 0.40% for the purpose of further suppressing the generation of whiskers.
- the Co content is not less than 0.01% but less than 8%.
- Co is an element that influences the suppression of generation of whiskers and the occurrence of fractures and cracks. With a Co content of less than 0.01%, the effect of suppressing the generation of whiskers is not exhibited, while with a Co content of not less than 8%, fractures or cracks should occur in a surface of a plating film by external stresses.
- the Co content is preferably not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably greater than 0.1% for the purpose of further suppressing the generation of whiskers.
- the total content of Ni and Co is less than 9.5%.
- each of the Ni content and the Co content is greater than 0%, and at least one of the requirement that the Ni content is not less than 0.03% and the requirement that the Co content is not less than 0.010% is satisfied.
- the Co content is preferably not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping.
- the Ni content is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping.
- the Ni content be not greater than 0.6% and the Co content be not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping.
- the total content of Ni and Co is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably greater than 0.1% for the purpose of further suppressing the generation of whiskers.
- the solder alloy of the invention can sufficiently suppress the generation of external stress-type whiskers and therefore can be suitably used as an electric contact that establishes electric continuity by mechanical joining, in a fitting type connection terminal.
- solder alloy of the invention is used preferably for a connector pin (metal terminal) of a connector and a terminal connecting portion (joint area) of a flexible flat cable (FFC) to be fitted with a connector.
- An electronic component comprises a metal substrate and a plating film formed in a joint area of the metal substrate, wherein the plating film contains Sn and Ni, the Ni content is not less than 0.06 wit% but not greater than 5.0 wt%, and the balance is Sn.
- An electronic component comprises a metal substrate and a plating film formed in a joint area of the metal substrate, wherein the plating film contains Sn and Co, the Co content is not less than 0.01 wt% but less than 8 wt%, and the balance is Sn.
- An electronic component comprises a metal substrate and a plating film formed in a joint area of the metal substrate, wherein the plating film contains Sn, Ni and Co, the total content of Ni and Co is less than 9.5 wt%, the Ni content and the Co content are each greater than 0 wt% and at least one of the requirement that the Ni content is not less than 0.03 wt% and the requirement that the Co content is not less than 0.010 wt% is satisfied, and the balance is Sn.
- the electronic components according to the first to third embodiments of the invention each have a plating film containing, in addition to Sn, a specific amount(s) of Ni and/or Co as described above, thereby suppressing the generation of external stress-type whiskers at a surface of the plating film.
- a metal substrate included in the electronic component of the invention is not particularly limited, and preferred examples thereof include a metal substrate constituting a terminal connecting portion (joint area) of a flexible flat cable (FFC) mentioned above and a metal substrate constituting an electrode.
- FFC flexible flat cable
- the metal substrate above include a Cu substrate, a Ni substrate and a Au substrate.
- a Cu substrate is preferably used and a substrate obtained by Ni-plating a surface of a Cu substrate, which serves as a core, is more preferably used because a plating film formed from the solder alloy of the invention can be easily formed.
- the thickness of the metal substrate is not particularly limited, and is preferably 0.05 to 0.5 mm for the purpose of ensuring the strength of the electronic component and decreasing the thickness.
- a plating film included in the electronic component of the invention is a plating film that is formed in a joint area of the metal substrate and contains Sn and an element(s) as specified in the first to third embodiments to be described below in detail.
- the Ni content is not less than 0.06% but not greater than 5.0%.
- Ni is an element that influences the suppression of generation of whiskers and the occurrence of fractures and cracks. With a Ni content of less than 0.06%, the effect of suppressing the generation of whiskers is not exhibited.
- the Ni content is preferably less than 5.0% for the sake of, inter alia, heat resistance of an electronic component in cases where a plating film is formed by hot dipping and appearance of a plating film in cases where the plating film is formed by electroplating.
- the Ni content is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably not less than 0.40% for the purpose of further suppressing the generation of whiskers.
- the Co content is not less than 0.01% but less than 8%.
- Co is an element that influences the suppression of generation of whiskers and the occurrence of fractures and cracks. With a Co content of less than 0.01%, the effect of suppressing the generation of whiskers is not exhibited, while with a Co content of not less than 8%, fractures or cracks should occur in a surface of a plating film by external stresses.
- the Co content is preferably not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably greater than 0.1% for the purpose of further suppressing the generation of whiskers.
- the total content of Ni and Co is less than 9.5%.
- each of the Ni content and the Co content is greater than 0%, and at least one of the requirement that the Ni content is not less than 0.03% and the requirement that the Co content is not less than 0.010% is satisfied.
- the Co content is preferably not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping.
- the Ni content is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping.
- the Ni content be not greater than 0.6% and the Co content be not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping.
- the total content of Ni and Co is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably greater than 0.1% for the purpose of further suppressing the generation of whiskers.
- the method of forming a plating film is not particularly limited, and exemplary methods include conventionally known plating methods such as hot dipping involving preparing the solder alloy of the invention and then melting the prepared solder alloy in, for instance, a jet solder bath to carry out plating, and electroplating involving carrying out plating with an electroplating device using one or more types of plating solutions such that the resultant plating film can have composition falling within the ranges defined above in the first to third embodiments.
- the electronic component of the invention is capable of suppressing the generation of external stress-type whiskers not only when the plating film is formed from the solder alloy of the invention by hot dipping but also when the plating film is formed in the electronic component by electroplating such that the resultant plating film can have composition falling within the ranges defined above in the first to third embodiments.
- the thickness of the plating film is not particularly limited, and is preferably 10 to 30 ⁇ m in the case of hot dipping and preferably 1 to 5 ⁇ m in the case of electroplating.
- solder alloy of the invention is described in detail below by way of examples. However, the present invention is not limited thereto.
- each Ni-plated Cu sheet (size: 30 mm x 30 mm x 0.3 mm; Ni-plating thickness: 3 ⁇ m) was subjected to hot dipping to form a plating film (thickness: 10 ⁇ m). After hot dipping, each sheet was rinsed with isopropyl alcohol (IPA) for 1 minute and subjected to ultrasonic cleaning with acetone for 5 minutes to remove flux residue.
- IPA isopropyl alcohol
- a device used in hot dipping and plating conditions are as follows.
- Solder Checker SAT-5200 (manufactured by RHESCA Co., Ltd.)
- Ni-plated Cu sheet size: 30 mm x 30 mm x 0.3 mm; Ni-plating thickness: 3 ⁇ m
- a carbon sheet used as the anode immersed in a beaker having therein a plating solution having been prepared to form a plating film having alloy composition shown in Tables 1 to 4, and current was applied to carry out electroplating, thereby forming a plating film (thickness: 5 ⁇ m).
- Raw materials and the composition of the plating solution, the current density in plating, the bath temperature inside the beaker, and the time for which current was applied (plating time) were suitably adjusted for each of Reference examples, Examples and Comparative examples by conventionally known methods.
- the length of an external stress-type whisker was measured by a ball indenter process according to "Whisker test methods for electronic connectors" defined in JEITA RC-5241. The measurement was performed at given three positions in each sample, and a whisker with the maximum length was measured. In plating films formed in Comparative examples 2, 5 to 8, 12 and 13, cracks occurred through the ball indenter process due to a large amount of Ni and/or Co present in the plating films and accordingly, the measurement of whisker length was not performed.
- a load tester that satisfies the specifications defined in "4.4 Load tester” of JEITA RC-5241 (Diameter of a zirconia ball indenter: 1 mm)
- a sample having a plating film formed of a solder alloy (Sn-0.4Ni) prepared in Example 5 was cut by means of a focused ion beam (FIB) to obtain cross sections at an indentation and its periphery.
- FIG. 2 an image of a surface of a plating film formed of a solder alloy (Sn-0.3Co) prepared in Example 15 at the area including an indentation and its periphery and images of cross sections obtained at the indentation and its periphery, as taken with a scanning electron microscope (SEM), are shown in FIG. 2 .
- Sn-0.3Co solder alloy
- solder alloy with a maximum whisker length of not greater than 30 ⁇ m is classified as an Example, while a solder alloy with a maximum whisker length of greater than 30 ⁇ m and a solder alloy with a maximum whisker length of not greater than 30 ⁇ m but allowing cracks to occur in the resultant plating are classified as Comparative example.
- the result shown in FIG. 3 revealed that when the Ni content was not greater than 0.6%, the zero cross time was short and thus, wettability was good.
- the result shown in FIG. 4 revealed that when the Co content was not greater than 0.4%, the zero cross time was short and thus, wettability was good.
- the results shown in FIG. 5 revealed that also when Ni and Co were contained, if the Ni content was not greater than 0.6% or the Co content was not greater than 0.4%, wettability was good.
- a tester and test conditions used in the evaluation are as follows.
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Abstract
Description
- The present invention relates to a solder alloy for plating used for an electric contact that establishes electric continuity by mechanical joining, particularly to a solder alloy for plating and an electronic component used in a fitting type connection terminal.
- Conventionally, surfaces of wiring materials, particularly wiring materials made of copper or a copper alloy are plated with tin (Sn), silver (Ag), gold (Au) or nickel (Ni) in order to prevent the wiring materials from oxidizing. In particular, Sn is inexpensive, and owing to its softness, readily deforms when receiving pressure upon fitting (contacting), leading to an increased contact area and a lower contact resistance. Accordingly, wiring materials with Sn-plated surfaces are widely and typically used.
- As alloys for such Sn plating, use of Pb-free materials and non-halogen materials has been recently required from an environmental viewpoint, and various materials used for wiring materials are also required to be Pb-free or halogen-free.
- It is known that there is a problem in that, as Sn plating is made Pb-free, particularly in Sn- or Sn alloy-plating, whiskers that are needle-like crystals of Sn are generated from plating, which may cause a short circuit between adjacent wiring materials.
- In connection with whiskering, it gradually becomes apparent that a portion (electric contact) to which an external stress is applied through mechanical joining (e.g., fitting, pressing, inserting and caulking) cannot avoid such whiskering even when the portion undergoes reflow treatment.
- In this description, a whisker generated at an electric contact due to an external stress applied through mechanical joining is also called "external stress-type whisker."
- As other types of whiskers generated due to different causes from those of generation of external stress-type whiskers, known are an "internal stress-type whisker (naturally-generated whisker)" generated due to volume expansion associated with the growth of an intermetallic compound in Sn plating, a "temperature cycle-type whisker" generated due to a compressive stress resulting from the difference in thermal expansion between a substrate and Sn plating, and an "oxidation/corrosion-type whisker" generated due to a compressive stress resulting from oxidation or corrosion of Sn in a high temperature and high humidity environment.
-
Patent Literature 1 describes, as a solder alloy capable of eliminating the problem associated with external stress-type whiskers, "a Pb-free solder alloy comprising: Ag of 0.1 to 5 wt%; Cu of 0.1 to 5 wt%; a first dopant of not more than 10 wt%, the first dopant comprising at least one element selected from a group consisted of Sb, Bi, Cd, In, Ag, Au, Ni, Ti, Zr, and Hf; a second dopant of not more than 10 wt%, and the second dopant comprising at least one element selected from a group consisted of Ge, Zn, P, K, Cr, Mn, Na, V, Si, Al, Li, Mg and Ca; and Sn as a remaining part" ([claim 10]). -
Patent Literature 2 describes "a Pb-free solder alloy comprising: not less than 0.1 wt% but not more than 3.5 wt% of Ag; not less than 0.1 wt% but not more than 3.5 wt% of Cu; not less than 0.002 wt% but not more than 0.5 wt% of Zn; and the balance of Sn" and "the Pb-free solder alloy obtained by adding at least one of P, Ge, K, Cr, Mn, Na, V, Si, Ti, Al, Li, Mg, Ca and Zr as an oxidation control element" ([claim 10] and [claim 11]). -
- Patent Literature 1:
JP 2008-031550 A - Patent Literature 2:
JP 2011-192652 A - The present inventors have made a study on the Pb-free solder alloys described in
Patent Literatures - An object of the present invention is therefore to provide a solder alloy for plating and an electronic component that are capable of suppressing the generation of external stress-type whiskers.
- The present inventors have made an intensive study to achieve the object above and found that by adding a specific amount(s) of Ni and/or Co in addition to Sn, the generation of external stress-type whiskers can be suppressed. The invention has been thus completed.
- Accordingly, the present inventors found that the object can be achieved by the characteristic features as described below.
- [1] A solder alloy for plating used for an electric contact that establishes electric continuity by mechanical joining, the solder alloy comprising Sn and Ni,
wherein a Ni content is not less than 0.06 wt% but not greater than 5.0 wt%, and
a balance is Sn. - [2] A solder alloy for plating used for an electric contact that establishes electric continuity by mechanical joining, the solder alloy comprising Sn and Co,
wherein a Co content is not less than 0.01 wt% but less than 8 wt%, and
a balance is Sn. - [3] A solder alloy for plating used for an electric contact that establishes electric continuity by mechanical joining, the solder alloy comprising Sn, Ni and Co,
wherein a total content of Ni and Co is less than 9.5 wit%,
a Ni content and a Co content are each greater than 0 wt% and at least one of a requirement that the Ni content is not less than 0.03 wt% and a requirement that the Co content is not less than 0.010 wt% is satisfied, and
a balance is Sn. - [4] The solder alloy for plating according to any one of claims [1] to [3], wherein the solder alloy is used in a fitting type connection terminal.
- [5] An electronic component comprising a metal substrate and a plating film formed in a joint area of the metal substrate,
wherein the plating film contains Sn and Ni,
a Ni content is not less than 0.06 wt% but not greater than 5.0 wt%, and
a balance is Sn. - [6] An electronic component comprising a metal substrate and a plating film formed in a joint area of the metal substrate,
wherein the plating film contains Sn and Co,
a Co content is not less than 0.01 wt% but less than 8 wt%, and
a balance is Sn. - [7] An electronic component comprising a metal substrate and a plating film formed in a joint area of the metal substrate,
wherein the plating film contains Sn, Ni and Co,
a total content of Ni and Co is less than 9.5 wt%,
a Ni content and a Co content are each greater than 0 wt% and at least one of a requirement that the Ni content is not less than 0.03 wt% and a requirement that the Co content is not less than 0.010 wt% is satisfied, and
a balance is Sn. - As described below, the present invention is able to provide a solder alloy for plating and an electronic component that are capable of suppressing the generation of external stress-type whiskers.
-
- [
FIG. 1] FIG. 1(A) is a scanning electron microscope (SEM) image of an indentation and its periphery of a plating film formed of a solder alloy (Sn-0.4Ni) prepared in Example 5;FIG. 1(B) is an SEM image of a cross section taken along the white line inFIG. 1(A) as observed in the direction of arrow B;FIG. 1(C) is an SEM image of a cross section taken along the other white line inFIG. 1(A) as observed in the direction of arrow C;FIG. 1(D) is an enlarged photograph of the region surrounded by the white line inFIG. 1(B); and FIG. 1(E) is an enlarged photograph of the region surrounded by the white line inFIG. 1(C) . - [
FIG. 2] FIG. 2(A) is a scanning electron microscope (SEM) image of an indentation and its periphery of a plating film formed of a solder alloy (Sn-0.3Co) prepared in Example 15;FIG. 2(B) is an SEM image of a cross section taken along the white line inFIG. 2(A) as observed in the direction of arrow B;FIG. 2(C) is an SEM image of a cross section taken along the other white line inFIG. 2(A) as observed in the direction of arrow C; andFIG. 2(D) is an enlarged photograph of the region surrounded by the white line inFIG. 2(B) . - [
FIG. 3] FIG. 3 is a graph showing the relationship between the Ni content and the zero cross time for a solder alloy containing Sn and Ni. - [
FIG. 4] FIG. 4 is a graph showing the relationship between the Co content and the zero cross time for a solder alloy containing Sn and Co. - [
FIG. 5] FIGS. 5(A) and 5(B) are graphs each showing a relationship between the Ni and Co content and the zero cross time for a solder alloy containing Sn, Ni and Co. - The solder alloy for plating and the electronic component according to the invention are described below.
- In this description, any numerical range using "to" refers to a numerical range including the values stated before and after "to" as the upper and lower limits, and the sign "%" for the content refers to % by mass.
- A solder alloy for plating according to a first embodiment of the invention used for an electric contact that establishes electric continuity by mechanical joining, comprises Sn and Ni, wherein the Ni content is not less than 0.06 wt% but not greater than 5.0 wt%, and the balance is Sn.
- A solder alloy for plating according to a second embodiment of the invention used for an electric contact that establishes electric continuity by mechanical joining, comprises Sn and Co, wherein the Co content is not less than 0.01 wt% but less than 8 wt%, and the balance is Sn.
- A solder alloy for plating according to a third embodiment of the invention used for an electric contact that establishes electric continuity by mechanical joining, comprises Sn, Ni and Co, wherein the total content of Ni and Co is less than 9.5 wt%, the Ni content and the Co content are each greater than 0 wt% and at least one of the requirement that the Ni content is not less than 0.03 wt% and the requirement that the Co content is not less than 0.010 wt% is satisfied, and the balance is Sn.
- When the solder alloys according to the first to third embodiments of the invention (hereinafter collectively called "solder alloy of the invention") each contain a specific amount(s) of Ni and/or Co in addition to Sn, the generation of external stress-type whiskers is suppressed.
- Although not evident for details, the mechanism of this is assumed as below.
- First, the present inventors assumed that external stress-type whiskers are generated because Sn atoms contained in a plating film are dispersed due to a mechanical stress applied from the outside and subsequently, the Sn atoms are recrystallized, resulting in the generation of whiskers, which are whisker-like crystals.
- The present inventors then assumed that when a specific amount(s) of Ni and/or Co is contained in addition to Sn, a Sn-Ni compound, a Sn-Co compound or a Sn-Ni-Co compound is to be present in a plating film, which serves to inhibit the dispersion of Sn atoms, leading to a decrease in growth and even generation of whiskers.
- This assumption can be made also from the results obtained from cross sections of plating films formed of solder alloys prepared in Examples to be described later.
- In addition, the present inventors found that, with Sn plating using a solder alloy containing a specific small amount of Ni, the generation of internal stress-type whiskers mentioned above is unable to be suppressed. Considering this finding, it can be said that the fact that the solder alloy of the invention brings about the effect of suppressing the generation of external stress-type whiskers is totally unforeseeable.
- Alloy compositions of the solder alloy of the invention are described in detail below.
- In the first embodiment of the invention, the Ni content is not less than 0.06% but not greater than 5.0%.
- Ni is an element that influences the suppression of generation of whiskers and the occurrence of fractures and cracks. With a Ni content of less than 0.06%, the effect of suppressing the generation of whiskers is not exhibited.
- In the present invention, the Ni content is preferably less than 5.0% for the sake of, inter alia, heat resistance of an electronic component in cases where a plating film is formed by hot dipping and appearance of a plating film in cases where the plating film is formed by electroplating.
- The Ni content is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably not less than 0.40% for the purpose of further suppressing the generation of whiskers.
- In the second embodiment of the invention, the Co content is not less than 0.01% but less than 8%.
- Co is an element that influences the suppression of generation of whiskers and the occurrence of fractures and cracks. With a Co content of less than 0.01%, the effect of suppressing the generation of whiskers is not exhibited, while with a Co content of not less than 8%, fractures or cracks should occur in a surface of a plating film by external stresses.
- In the present invention, the Co content is preferably not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably greater than 0.1% for the purpose of further suppressing the generation of whiskers.
- In the third embodiment of the invention, the total content of Ni and Co is less than 9.5%.
- In the third embodiment in which Ni and Co are contained, each of the Ni content and the Co content is greater than 0%, and at least one of the requirement that the Ni content is not less than 0.03% and the requirement that the Co content is not less than 0.010% is satisfied.
- When the requirement that the Ni content is not less than 0.03% is satisfied, the Co content is preferably not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping.
- When the requirement that the Co content is not less than 0.010% is satisfied, the Ni content is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping.
- When the requirement that the Ni content is not less than 0.03% and the requirement that the Co content is not less than 0.010% are both satisfied, it is preferable that the Ni content be not greater than 0.6% and the Co content be not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping.
- The total content of Ni and Co is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably greater than 0.1% for the purpose of further suppressing the generation of whiskers.
- The solder alloy of the invention can sufficiently suppress the generation of external stress-type whiskers and therefore can be suitably used as an electric contact that establishes electric continuity by mechanical joining, in a fitting type connection terminal.
- Specifically, the solder alloy of the invention is used preferably for a connector pin (metal terminal) of a connector and a terminal connecting portion (joint area) of a flexible flat cable (FFC) to be fitted with a connector.
- An electronic component of the invention is described in detail below.
- An electronic component according to a first embodiment of the invention comprises a metal substrate and a plating film formed in a joint area of the metal substrate, wherein the plating film contains Sn and Ni, the Ni content is not less than 0.06 wit% but not greater than 5.0 wt%, and the balance is Sn.
- An electronic component according to a second embodiment of the invention comprises a metal substrate and a plating film formed in a joint area of the metal substrate, wherein the plating film contains Sn and Co, the Co content is not less than 0.01 wt% but less than 8 wt%, and the balance is Sn.
- An electronic component according to a third embodiment of the invention comprises a metal substrate and a plating film formed in a joint area of the metal substrate, wherein the plating film contains Sn, Ni and Co, the total content of Ni and Co is less than 9.5 wt%, the Ni content and the Co content are each greater than 0 wt% and at least one of the requirement that the Ni content is not less than 0.03 wt% and the requirement that the Co content is not less than 0.010 wt% is satisfied, and the balance is Sn.
- The electronic components according to the first to third embodiments of the invention (hereinafter collectively called "electronic component of the invention") each have a plating film containing, in addition to Sn, a specific amount(s) of Ni and/or Co as described above, thereby suppressing the generation of external stress-type whiskers at a surface of the plating film.
- In this regard, the mechanism of suppression of generation of external stress-type whiskers should be the same as that described for the solder alloy of the invention as above and is therefore not described.
- The configuration of the electronic component of the invention is described in detail below.
- A metal substrate included in the electronic component of the invention is not particularly limited, and preferred examples thereof include a metal substrate constituting a terminal connecting portion (joint area) of a flexible flat cable (FFC) mentioned above and a metal substrate constituting an electrode.
- Specific examples of the metal substrate above include a Cu substrate, a Ni substrate and a Au substrate. A Cu substrate is preferably used and a substrate obtained by Ni-plating a surface of a Cu substrate, which serves as a core, is more preferably used because a plating film formed from the solder alloy of the invention can be easily formed.
- The thickness of the metal substrate is not particularly limited, and is preferably 0.05 to 0.5 mm for the purpose of ensuring the strength of the electronic component and decreasing the thickness.
- A plating film included in the electronic component of the invention is a plating film that is formed in a joint area of the metal substrate and contains Sn and an element(s) as specified in the first to third embodiments to be described below in detail.
- In the first embodiment of the invention, the Ni content is not less than 0.06% but not greater than 5.0%.
- Ni is an element that influences the suppression of generation of whiskers and the occurrence of fractures and cracks. With a Ni content of less than 0.06%, the effect of suppressing the generation of whiskers is not exhibited.
- In the present invention, the Ni content is preferably less than 5.0% for the sake of, inter alia, heat resistance of an electronic component in cases where a plating film is formed by hot dipping and appearance of a plating film in cases where the plating film is formed by electroplating.
- The Ni content is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably not less than 0.40% for the purpose of further suppressing the generation of whiskers.
- In the second embodiment of the invention, the Co content is not less than 0.01% but less than 8%.
- Co is an element that influences the suppression of generation of whiskers and the occurrence of fractures and cracks. With a Co content of less than 0.01%, the effect of suppressing the generation of whiskers is not exhibited, while with a Co content of not less than 8%, fractures or cracks should occur in a surface of a plating film by external stresses.
- In the present invention, the Co content is preferably not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably greater than 0.1% for the purpose of further suppressing the generation of whiskers.
- In the third embodiment of the invention, the total content of Ni and Co is less than 9.5%.
- In the third embodiment in which Ni and Co are contained, each of the Ni content and the Co content is greater than 0%, and at least one of the requirement that the Ni content is not less than 0.03% and the requirement that the Co content is not less than 0.010% is satisfied.
- When the requirement that the Ni content is not less than 0.03% is satisfied, the Co content is preferably not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping.
- When the requirement that the Co content is not less than 0.010% is satisfied, the Ni content is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping.
- When the requirement that the Ni content is not less than 0.03% and the requirement that the Co content is not less than 0.010% are both satisfied, it is preferable that the Ni content be not greater than 0.6% and the Co content be not greater than 0.4% for the sake of wettability in cases where a plating film is formed by hot dipping.
- The total content of Ni and Co is preferably not greater than 0.6% for the sake of wettability in cases where a plating film is formed by hot dipping, and more preferably greater than 0.1% for the purpose of further suppressing the generation of whiskers.
- The method of forming a plating film (plating method) is not particularly limited, and exemplary methods include conventionally known plating methods such as hot dipping involving preparing the solder alloy of the invention and then melting the prepared solder alloy in, for instance, a jet solder bath to carry out plating, and electroplating involving carrying out plating with an electroplating device using one or more types of plating solutions such that the resultant plating film can have composition falling within the ranges defined above in the first to third embodiments.
- The electronic component of the invention is capable of suppressing the generation of external stress-type whiskers not only when the plating film is formed from the solder alloy of the invention by hot dipping but also when the plating film is formed in the electronic component by electroplating such that the resultant plating film can have composition falling within the ranges defined above in the first to third embodiments.
- The thickness of the plating film is not particularly limited, and is preferably 10 to 30 µm in the case of hot dipping and preferably 1 to 5 µm in the case of electroplating.
- The solder alloy of the invention is described in detail below by way of examples. However, the present invention is not limited thereto.
- Using solder alloys having alloy composition shown in Tables 1 to 4 below, each Ni-plated Cu sheet (size: 30 mm x 30 mm x 0.3 mm; Ni-plating thickness: 3 µm) was subjected to hot dipping to form a plating film (thickness: 10 µm). After hot dipping, each sheet was rinsed with isopropyl alcohol (IPA) for 1 minute and subjected to ultrasonic cleaning with acetone for 5 minutes to remove flux residue.
- A device used in hot dipping and plating conditions are as follows.
- Solder Checker SAT-5200 (manufactured by RHESCA Co., Ltd.)
-
- Immersion rate: 5 mm/s
- Immersion depth: 20 mm
- Immersion time: 7 seconds
- Solder bath temperature: 250°C to 400°C
- Flux for use: ES-1090 (manufactured by Senju Metal Industry Co., Ltd.)
- Each Ni-plated Cu sheet (size: 30 mm x 30 mm x 0.3 mm; Ni-plating thickness: 3 µm) was, along with a carbon sheet used as the anode, immersed in a beaker having therein a plating solution having been prepared to form a plating film having alloy composition shown in Tables 1 to 4, and current was applied to carry out electroplating, thereby forming a plating film (thickness: 5 µm).
- Raw materials and the composition of the plating solution, the current density in plating, the bath temperature inside the beaker, and the time for which current was applied (plating time) were suitably adjusted for each of Reference examples, Examples and Comparative examples by conventionally known methods.
- For each Ni-plated Cu sheet on which a plating film was formed, the length of an external stress-type whisker was measured by a ball indenter process according to "Whisker test methods for electronic connectors" defined in JEITA RC-5241. The measurement was performed at given three positions in each sample, and a whisker with the maximum length was measured. In plating films formed in Comparative examples 2, 5 to 8, 12 and 13, cracks occurred through the ball indenter process due to a large amount of Ni and/or Co present in the plating films and accordingly, the measurement of whisker length was not performed.
- A device and conditions for the test and a device and conditions for measurement of whisker length are stated below.
- As a result of the measurement, when the maximum whisker length was not greater than 30 µm, the generation of external stress-type whiskers was determined to have been suppressed and this was evaluated as "good." When the maximum whisker length was greater than 30 µm, the generation of external stress-type whiskers was determined not to have been suppressed and this was evaluated as "poor."
- The measurements of maximum whisker lengths and the evaluation results are shown in Tables 1 to 4 below.
- A load tester that satisfies the specifications defined in "4.4 Load tester" of JEITA RC-5241 (Diameter of a zirconia ball indenter: 1 mm)
-
- Load: 300 g
- Test period: 10 days (240 hours)
-
- FE-SEM: Quanta FEG250 (manufactured by FEI)
- Acceleration voltage: 10 kV
- Of samples subjected to the whisker test through the ball indenter process, a sample having a plating film formed of a solder alloy (Sn-0.4Ni) prepared in Example 5 was cut by means of a focused ion beam (FIB) to obtain cross sections at an indentation and its periphery. An image of a surface of the plating film at the area including the indentation and its periphery and images of cross sections obtained at the indentation and its periphery, as taken with an SMI3050SE scanning electron microscope (SEM) (manufactured by Hitachi High-Tech Science Corporation), are shown in
FIG. 1 . - Similarly, an image of a surface of a plating film formed of a solder alloy (Sn-0.3Co) prepared in Example 15 at the area including an indentation and its periphery and images of cross sections obtained at the indentation and its periphery, as taken with a scanning electron microscope (SEM), are shown in
FIG. 2 . - As can be seen from the cross sections of the plating films shown in
FIGS. 1 and2 , needle-like crystals (surrounded by broken lines) can be observed inside the plating films. As a result of analyses of these crystals using energy dispersive X-ray spectrometry (EDS), Sn and Ni were detected from the plating film (Sn-0.4Ni), and Sn and Co were detected from the plating film (Sn-0.3Co). - In this description, a solder alloy with a maximum whisker length of not greater than 30 µm is classified as an Example, while a solder alloy with a maximum whisker length of greater than 30 µm and a solder alloy with a maximum whisker length of not greater than 30 µm but allowing cracks to occur in the resultant plating are classified as Comparative example.
[Table 1] Table 1 Alloy composition (% by weight) Type of plating Maximum whisker Sn Pb Length (µm) Evaluation Reference example 1 100 Hot dipping 36 Poor Reference example 2 Balance 10 15 Good Reference example 3 100 Electroplating 56 Poor [Table 2] Table 2 Alloy composition (% by weight) Type of plating Maximum whisker Sn Ni Length (µm) Evaluation Comparative example 1 Balance 0.05 Hot dipping 47 Poor Example 1 Balance 0.06 23 Good Example 2 Balance 0.07 23 Good Example 3 Balance 0.10 27 Good Example 4 Balance 0.30 20 Good Example 5 Balance 0.40 10 Good Example 6 Balance 0.50 Electroplating 8 Good Example 7 Balance 1.00 17 Good Example 8 Balance 3.00 11 Good Example 9 Balance 4.00 14 Good Example 10 Balance 5.00 7 Good Comparative example 2 Balance 10.00 - - [Table 3] Table 3 Alloy composition (% by weight) Type of plating Maximum whisker Sn Co Length (µm) Evaluation Comparative example 3 Balance 0.005 Hot dipping 36 Poor Comparative example 4 Balance 0.007 36 Poor Example 11 Balance 0.01 20 Good Example 12 Balance 0.03 19 Good Example 13 Balance 0.10 13 Good Example 14 Balance 0.10 Electroplating 19 Good Example 15 Balance 0.30 Hot dipping 10 Good Example 16 Balance 1.00 Electroplating 16 Good Example 17 Balance 3.00 10 Good Example 18 Balance 5.00 5 Good Example 19 Balance 7.00 3 Good Comparative example 5 Balance 8.00 - - Comparative example 6 Balance 9.90 - - Comparative example 7 Balance 10.00 - - - Comparative example 8 Balance 26.00 - - [Table 4] Table 4 Alloy composition (% by weight) Type of plating Maximum whisker Total content of Ni+Co Sn Ni Co Length (µm) Evaluation Comparative example 9 Balance 0.02 0.005 Hot dipping 39 Poor 0.025 Comparative example 10 Balance 0.002 0.008 35 Poor 0.01 Comparative example 11 Balance 0.003 0.007 35 Poor 0.01 Example 20 Balance 0.01 0.01 21 Good 0.02 Example 21 Balance 0.005 0.02 12 Good 0.025 Example 22 Balance 0.03 0.005 16 Good 0.035 Example 23 Balance 0.4 0.005 20 Good 0.045 Example 24 Balance 0.005 0.04 14 Good 0.045 Example 25 Balance 0.30 0.90 Electroplating 26 Good 1.2 Example 26 Balance 1.50 0.70 14 Good 2.2 Example 27 Balance 1.10 1.80 11 Good 2.9 Example 28 Balance 2.70 1.10 7 Good 3.8 Example 29 Balance 4.00 3.40 12 Good 7.4 Comparative example 12 Balance 5.20 4.30 - - 9.5 Comparative example 13 Balance 3.70 5.80 - - 9.5 - The results shown in Tables 1 to 4 revealed that an alloy containing a small amount of Ni or Co suppressed the maximum whisker length less than the alloys prepared in Reference examples 1 and 2 (Comparative examples 1, 3 and 4).
- It was also revealed that an alloy containing Ni and Co in which the amount of Ni or Co was small suppressed the maximum whisker length less than the alloys prepared in Reference examples 1 and 2 (Comparative examples 9 to 11).
- Aside from that, the result of Reference example 3 revealed that an alloy free from Ni and Co did not suppress the maximum whisker length even through electroplating.
- Further, it was revealed that an alloy containing a large amount(s) of Ni and/or Co suppressed the generation of whiskers but a crack occurred in a plating film along an indentation. Thus, the alloy is not suitable for use in fitting application (Comparative examples 2, 5 to 8, 12 and 13).
- In contrast, it was revealed that with an alloy in which the Ni content, the Co content or the total content of Ni and Co (when both were contained) was within the relevant specified range, the maximum whisker length was suppressed better than the alloy prepared in Reference examples 1 (Examples 1 to 5, 11 to 13, 15 and 20 to 24). This result was observed similarly in cases where a plating film was formed by electroplating (Examples 6 to 10, 14, 16 to 19 and 25 to 29).
- In particular, it was revealed from the comparison of Examples 1 to 5 that when the Ni content was greater than 0.30 wt%, the maximum whisker length was 10 µm, and the generation of whiskers was suppressed better than the case of using the Sn-Pb alloy (Reference example 2) that had been conventionally recognized as having a good whiskering resistance.
- Likewise, it was revealed from the comparison of Examples 11 to 15 that when the Co content was greater than 0.10 wt%, the maximum whisker length was 10 µm, and the generation of whiskers was suppressed better than the case of using the Sn-Pb alloy (Reference example 2) that had been conventionally recognized as having a good whiskering resistance.
- When the metal substrate on which a plating film is formed is changed to a "Cu sheet without Ni-plating," the same tendencies as those of Examples 1 to 29 were seen.
- For each solder alloy containing, in addition to Sn, Ni and/or Co, the zero cross time was measured by a wetting balance method according to JIS Z 3198-4. The results are shown in
FIGS. 3 to 5 . - The result shown in
FIG. 3 revealed that when the Ni content was not greater than 0.6%, the zero cross time was short and thus, wettability was good. Likewise, the result shown inFIG. 4 revealed that when the Co content was not greater than 0.4%, the zero cross time was short and thus, wettability was good. In addition, the results shown inFIG. 5 revealed that also when Ni and Co were contained, if the Ni content was not greater than 0.6% or the Co content was not greater than 0.4%, wettability was good. - A tester and test conditions used in the evaluation are as follows.
-
- Solder Checker SAT-5200 (manufactured by RHESCA Co., Ltd.)
-
- Immersion rate: 10 mm/s
- Immersion depth: 2 mm
- Immersion time: 5 seconds
- Solder bath temperature: 250°C
- Flux for use: ES-1090 (manufactured by Senju Metal Industry Co., Ltd.)
- Cu sheet for use: 30 mm x 3 mm
Claims (7)
- A solder alloy for plating used for an electric contact that establishes electric continuity by mechanical joining, the solder alloy comprising Sn and Ni,
wherein a Ni content is not less than 0.06 wt% but not greater than 5.0 wt%, and
a balance is Sn. - A solder alloy for plating used for an electric contact that establishes electric continuity by mechanical joining, the solder alloy comprising Sn and Co,
wherein a Co content is not less than 0.01 wt% but less than 8 wt%, and
a balance is Sn. - A solder alloy for plating used for an electric contact that establishes electric continuity by mechanical joining, the solder alloy comprising Sn, Ni and Co,
wherein a total content of Ni and Co is less than 9.5 wt%,
a Ni content and a Co content are each greater than 0 wt% and at least one of a requirement that the Ni content is not less than 0.03 wt% and a requirement that the Co content is not less than 0.010 wt% is satisfied, and
a balance is Sn. - The solder alloy for plating according to any one of claims 1 to 3, wherein the solder alloy is used in a fitting type connection terminal.
- An electronic component comprising a metal substrate and a plating film formed in a joint area of the metal substrate,
wherein the plating film contains Sn and Ni,
a Ni content is not less than 0.06 wt% but not greater than 5.0 wt%, and
a balance is Sn. - An electronic component comprising a metal substrate and a plating film formed in a joint area of the metal substrate,
wherein the plating film contains Sn and Co,
a Co content is not less than 0.01 wt% but less than 8 wt%, and
a balance is Sn. - An electronic component comprising a metal substrate and a plating film formed in a joint area of the metal substrate,
wherein the plating film contains Sn, Ni and Co,
a total content of Ni and Co is less than 9.5 wt%,
a Ni content and a Co content are each greater than 0 wt% and at least one of a requirement that the Ni content is not less than 0.03 wt% and a requirement that the Co content is not less than 0.010 wt% is satisfied, and
a balance is Sn.
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JP2018153834A (en) * | 2017-03-17 | 2018-10-04 | 株式会社ニーケプロダクツ | Method of performing torch soldering of aluminum members with each other, or of aluminum member with copper member |
CN115502604B (en) * | 2022-09-29 | 2023-07-18 | 安徽科技学院 | Solder for magnesium alloy, using method and soldering flux thereof |
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CA1045577A (en) * | 1973-08-20 | 1979-01-02 | Martin H. Pollack | Electrodeposition of bright tin-nickel alloy |
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JPS51140819A (en) * | 1975-05-30 | 1976-12-04 | Mitsubishi Metal Corp | Decorative ni-co-sn alloy and heat treatment and production methods th ereof |
JPH0825050B2 (en) * | 1993-06-08 | 1996-03-13 | 日本アルミット株式会社 | Lead-free solder alloy |
DE4443461C1 (en) * | 1994-12-07 | 1996-07-04 | Wieland Werke Ag | Copper@ (alloy) composite strip or wire material used in electromechanical or electrooptical applications |
JP3754152B2 (en) * | 1996-11-08 | 2006-03-08 | 田中電子工業株式会社 | Lead-free solder material and electronic parts using the same |
JP3953169B2 (en) * | 1997-12-26 | 2007-08-08 | 株式会社神戸製鋼所 | Manufacturing method of plating material for mating type connection terminal |
JP2000077253A (en) * | 1998-09-02 | 2000-03-14 | Murata Mfg Co Ltd | Electronic component, electronic component chip, and component manufacturing method |
US20020155024A1 (en) * | 2000-10-27 | 2002-10-24 | H-Technologies Group, Inc. | Lead-free solder compositions |
US20020187364A1 (en) * | 2001-03-16 | 2002-12-12 | Shipley Company, L.L.C. | Tin plating |
CA2380704A1 (en) * | 2002-03-22 | 2003-09-22 | Sun Industrial Limited | Environmental friendly lead-free fishing, diving and net weight alloys |
JP2006009039A (en) * | 2004-06-21 | 2006-01-12 | Rambo Chemicals (Hong Kong) Ltd | Tin based plating film in which growth of whisker is suppressed and forming method therefor |
JP5059292B2 (en) * | 2005-03-08 | 2012-10-24 | 株式会社神戸製鋼所 | Sn alloy plating excellent in suppressing whisker generation |
JP4817095B2 (en) * | 2005-10-03 | 2011-11-16 | 上村工業株式会社 | Whisker suppression surface treatment method |
CN101051535B (en) | 2006-04-06 | 2012-09-19 | 日立电线株式会社 | Wiring conductor, method for fabricating same, terminal connecting assembly, and pb-free solder alloy |
JP5376553B2 (en) | 2006-06-26 | 2013-12-25 | 日立金属株式会社 | Wiring conductor and terminal connection |
JP2008021501A (en) * | 2006-07-12 | 2008-01-31 | Hitachi Cable Ltd | Electrical part for wiring, manufacturing method thereof, and terminal connecting part |
US20100059576A1 (en) * | 2008-09-05 | 2010-03-11 | American Iron & Metal Company, Inc. | Tin alloy solder composition |
JP5086485B1 (en) * | 2011-09-20 | 2012-11-28 | Jx日鉱日石金属株式会社 | Metal material for electronic parts and method for producing the same |
JP5968668B2 (en) * | 2012-04-13 | 2016-08-10 | Jx金属株式会社 | Metal materials for electronic parts |
CN103978320B (en) * | 2014-05-27 | 2016-05-25 | 北京理工大学 | The low silver-colored series lead-free solder that a kind of particle adds |
-
2015
- 2015-12-09 ES ES15869874T patent/ES2764394T3/en active Active
- 2015-12-09 EP EP15869874.6A patent/EP3235588B1/en not_active Not-in-force
- 2015-12-09 KR KR1020187015848A patent/KR20180066268A/en active Search and Examination
- 2015-12-09 WO PCT/JP2015/084560 patent/WO2016098669A1/en active Application Filing
- 2015-12-09 US US15/536,344 patent/US20170348805A1/en not_active Abandoned
- 2015-12-09 KR KR1020177016456A patent/KR20170075800A/en active Search and Examination
- 2015-12-09 JP JP2016564812A patent/JP6379217B2/en not_active Expired - Fee Related
- 2015-12-09 CN CN201580068610.8A patent/CN107000131B/en not_active Expired - Fee Related
- 2015-12-15 TW TW104142088A patent/TWI647317B/en active
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JP6379217B2 (en) | 2018-08-22 |
KR20180066268A (en) | 2018-06-18 |
KR20170075800A (en) | 2017-07-03 |
TWI647317B (en) | 2019-01-11 |
TW201629239A (en) | 2016-08-16 |
EP3235588B1 (en) | 2019-11-06 |
CN107000131A (en) | 2017-08-01 |
WO2016098669A1 (en) | 2016-06-23 |
ES2764394T3 (en) | 2020-06-03 |
US20170348805A1 (en) | 2017-12-07 |
JPWO2016098669A1 (en) | 2017-06-15 |
EP3235588A4 (en) | 2018-06-20 |
CN107000131B (en) | 2019-03-19 |
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